Recension of boron nitride phase diagram based on high-pressure and high-temperature experiments

Cubic boron nitride and hexagonal boron nitride are the two predominant crystalline structures of boron nitride.They can interconvert under varying pressure and temperature conditions.However,this transformation requires overcoming significant potential barriers in dynamics,which poses great difficulty in determining the c-BN/h-BN phase boundary.This study used high-pressure in situ differential thermal measurements to ascertain the temperature of h-BN/c-BN conversion within the commonly used pressure range(3-6 GPa)for the industrial synthesis of c-BN to constrain the P-T phase boundary of h-BN/c-BN in the pressure-temperature range as much as possible.Based on the analysis of the experimental data,it is determined that the relationship between pressure and temperature conforms to the following equation:P=a+1/bT.Here,P denotes the pressure(GPa)and T is the temperature(K).The coefficients are a=-3.8±0.8 GPa and b=229.8±17.1 GPa/K.These findings call into question existing high-pressure and high-temperature phase diagrams of boron nitride,which seem to overstate the phase boundary temperature between c-BN and h-BN.The BN phase diagram obtained from this study can provide critical temperature and pressure condition guidance for the industrial synthesis of c-BN,thus optimizing synthesis efficiency and product performance.

Thermodynamic Study on the Compositions of Fluid Phases in the C-O-H System Under High Temperature and Pressure

Based on the fluid phase equilibrium of the C-O-H system, the compositions of var-ious fluid phases under high temperatures and pressures have been calculated in terms of the available thermodynamic data and new P-V-T data and on the assumption of PT = ΣPi in this paper. The results indicate that in this system there are 5 major fluid phases in different pro-portions at various T and P. CH4 is the dominant phase (about 70% ) under relatively lower T and P. Its proportion obviously decreases with increasing T, P and fo2. The results pro-vide sufficient theoretical grounds for discussing the possibility of CH4 formation and the physical-chemical conditions of its stable occurrence and proportion in the geological environment.

Pressure-Induced Metallization and Electrical Phase Diagram for Polycrystalline CaB_6 under High Pressure and Low Temperature

The electrical properties of polycrystaltine CaB6 are revealed by in-situ resistance measurements under high pressure and low temperature. Due to the existence of grain boundaries, polycrystalline CaB6 behaves with semiconducting transport properties, which is different from the semimetallic CaB6 single crystals. The temperaturedependent resistance measurement results show that before the structural phase transition at 12.3 GPa the high pressure first induces the metallization at 6.5 GPa for CAB6. Moreover, the phase diagram for CaB6 is drawn based on the investigated electric conducting properties and at least three different conducting phases are found even at moderate high pressure and low temperature, indicating that the electric nature of CaB6 is very sensitive to the environment.

Cubic anvil cell apparatus for high-pressure and low-temperature physical property measurements

We will build a cubic anvil cell （CAC） apparatus for high-pressure and low-temperature physical property measurements in the synergic extreme condition user facility （SECUF）. In this article, we first introduce the operating principle, the development history, and the current status of the CAC apparatus, and subsequently describe the design plan and technical targets for the CAC in SECUF. We will demonstrate the unique advantages of CAC, i.e., excellent pressure homogeneity and large hydrostatic pressure capacity, by summarizing our recent research progresses using CAC. Finally, we conclude by providing some perspectives on the applications of CAC in the related research fields.

Structures and Low Temperature Magnetic Anomalies of High Pressure RE_2CuO_4

A series of oxygen-doped RE_2CuO_4 (RE=Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm) was synthesized using high-pressure/oxygen-doped technique. The structures and low temperature magnetic properties were investigated. The XRD patterns indicate that the structures of high oxygen pressure RE_2CuO_4 (only for RE=Sm, Eu) samples are pure T′ phase, but when RE= Gd, Tb, Dy, Ho, Er, Tm, the structures turn to disorder. The magnetic anomalies that occurred at T^30 K are observed in high oxygen pressure RE_2CuO_4. It is found that the transition temperatures of weak ferromagnetic anomalies are nearly independent of the rare-earth components. Thus, the O-doping plays an important role in anomalous magnetic properties of RE_2CuO_(4+δ). The magnetic anomalies in RE_2CuO_4 are considered to be due to ferromagnetic clusters formed in the Cu-O plane after the oxygen doping.

Behaviors of Zn2GeO4 under high pressure and high temperature

The structural stability of Zn2GeO4 was investigated by in-situ synchrotron radiation angle dispersive x-ray diffraction. The pressure-induced amorphization is observed up to 10 GPa at room temperature. The high-pressure and hightemperature sintering experiments and the Raman spectrum measurement firstly were performed to suggest that the amorphization is caused by insufficient thermal energy and tilting Zn–O–Ge and Ge–O–Ge bond angles with increasing pressure,respectively. The calculated bulk modulus of Zn2GeO4 is 117.8 GPa from the pressure-volume data. In general, insights into the mechanical behavior and structure evolution of Zn2GeO4 will shed light on the micro-mechanism of the materials variation under high pressure and high temperature.

Two-step high-pressure high-temperature synthesis of nanodiamonds from naphthalene

Nanodiamonds have outstanding mechanical properties,chemical inertness,and biocompatibility,which give them potential in various applications.Current methods for preparing nanodiamonds often lead to products with impurities and uneven morphologies.We report a two-step high-pressure high-temperature(HPHT) method to synthesize nanodiamonds using naphthalene as the precursor without metal catalysts.The grain size of the diamonds decreases with increasing carbonization time(at constant pressure and temperature of 11.5 GPa and 700℃,respectively).This is discussed in terms of the different crystallinities of the carbon intermediates.The probability of secondary anvil cracking during the HPHT process is also reduced.These results indicate that the two-step method is efficient for synthesizing nanodiamonds,and that it is applicable to other organic precursors.

CALCULATIONS OF THE PHASE EQUILIBRIA AND CRITICAL CURVES WITH THE EQUATION OF STATE FOR BINARY MIXTURES

A rational equation of state of the perturbation type with a repulsion and attraction term has been applied to reproduce critical curves of six different binary systems up to high temperatures and pressures. A square well potential for intermolecular interaction is used. With pairwise combination rules for these potentials three adjustable parameters are needed. The experimental critical point and phase equilibrium data are compared with the values predicted using the equation of state. Good agreement is obtained for the analysis of the critical pressure composition data and molar volumes.

Progress in the Study on the Phase Equilibria of the CO2·H2O and CO2-HeO-NaCI Systems

To study the feasibility of CO2 geological sequestration,it is needed to understand the complicated mul- tiple-phase equilibrium and the densities of aqueous solution with CO2 and multi-ions under wide geological condi- tions(273.15—473.15K,0—60MPa),which are also essential for designing separation equipments in chemical or oil-related industries.For this purpose,studies on the relevant phase equilibria and densities are reviewed and ana- lyzed and the method to improve or modify the existing model is suggested in order to obtain more reliable pre- dictions in a wide temperature and pressure range.Besides,three different models(the electrolyte non random two-liquid(ELECNRTL),the electrolyte NRTL combining with Helgeson model(ENRTL-HG),Pitzer activity co- efficient model combining with Helgeson model(PITZ-HG))are used to calculate the vapor-liquid phase equilib- rium of CO2-H2O and CO2-H2O-NaCl systems.For CO2-H2O system,the calculation results agree with the experi- mental data very well at low and medium pressure(0—20MPa),but there are great discrepancies above 20MPa.For the water content at 473.15K,the calculated results agree with the experimental data quite well.For the CO2-H2O-NaCl system,the PITZ-HG model show better results than ELECNRTL and ENRTL-HG models at the NaCl concentration of 0.52mol·L -1 .Bur for the NaCl concentration of 3.997mol·L -1 ,using the ELECNRTL and ENRTL-HG models gives better results than using the PITZ-HG model.It is shown that available experimental data and the thermodynamic calculations can satisfy the needs of the calculation of the sequestration capacity in the temperature and pressure range for disposal of CO2 in deep saline aquifers.More experimental data and more accu- rate thermodynamic calculations are needed in high temperature and pressure ranges(above 398.15K and 31.5MPa).

Pressure-induced phase transitions in the ZrXY(X=Si,Ge,Sn;Y=S,Se,Te)family compounds

Pressure is an effective and clean way to modify the electronic structures of materials,cause structural phase transitions and even induce the emergence of superconductivity.Here,we predicted several new phases of the Zr XY family at high pressures using the crystal structures search method together with first-principle calculations.In particular,the Zr Ge S compound undergoes an isosymmetric phase transition from P4/nmm-I to P4/nmm-II at approximately 82 GPa.Electronic band structures show that all the high-pressure phases are metallic.Among these new structures,P4/nmm-II Zr Ge S and P4/mmm Zr Ge Se can be quenched to ambient pressure with superconducting critical temperatures of approximately 8.1 K and 8.0 K,respectively.Our study provides a way to tune the structure,electronic properties,and superconducting behavior of topological materials through pressure.

The effect of phase transition on the compressional wave velocity for a trachybasalt at high temperature and high pressure

Compressional wave velocities in a trachybasalt, from Yichuan County, Henan Province, have been measured at 2.0 GPa and up to 1 350℃ in a YJ-3000 t cubic-anvil highpressure apparatus. The run products have been gained at the same pressure but different temperatures. The observation of the thin sections of the run products indicates that, corresponding to the variation of the compressional wave velocity in the trachybasalt, the phase transition has taken place. The relationship between the change of the compressional wave velocity and the hydrous mineral dehydration, solid-solid phase transformation and partial melting has been discussed. The experimental data presented here are of great importance to elucidating the geological process in the earth’s interior.

P-wave velocities of alkaline olivine basalt at high pressure and temperature and its controlling factors

SEISMIC wave inversion is one of the most important means for us to recognize the compositionand structure of the Earth’s interior.Although the experimental techniques of elastic wave ve-locity measurement at in situ high pressure and temperature develop very fast in recent

Raman and luminescence studies on phase transition of EuNbO_4 under high pressure

Raman and luminescence studies on the phase transition of europium orthoniobates （EuNbO4） under high pressure were performed. The pressure dependent Raman spectra revealed that an irreversible phase transition from monoclinic phase to M＇-fergusonite phase of EuNbO4 occurred at 7.3 GPa, and the two phases coexisted over a pressure range from 7.3 to 13.7 GPa. An obvious discontinuity on luminescence intensity ratio between 5D0 →7F2 and 5D0→7F1 transitions was observed with increasing pressure, in- dicating also that a phase transition occurred at 7.3 GPa, which was in agreement with the high pressure Raman spectra data. Mean- while, the Raman and luminescence spectra in the temperature range of 20--300 K showed the structure stability at low temperatures.

An experimental study of phase transformations in olivine under pressure and temperature conditions corresponding to the mantle transition zone

High-pressure polymorphs of olivine (wadsleyite and ringwoodite) are major minerals in the mantle transition zone (MTZ).Phase transformations in olivine are important for a series of geodynamic problems such as the mineralogical and evolutionary history of the mantle,mantle convection patterns,and deep focus earthquakes in subduction zones.In this study,we examine phase transformations in olivine with two compositions,namely Mg 2 SiO 4 (Fo 100) and (Mg 0.9 Fe 0.1) 2 SiO 4 (Fo 90),at pressures between 14.1 and 20 GPa and a constant temperature of 1400°C,using the newly installed multi-anvil system at the Laboratory for Studies of the Earth's Deep Interior (SEDI),China University of Geosciences (Wuhan).At 14.1 GPa,Fo 90 transformed completely into the wadsleyite structure (β),while Fo 100 remained as olivine (α).Between 14.8 and 15.6 GPa,both Fo 100 and Fo 90 transformed into the wadsleyite structure.Wadsleyite crystals were identified by two characteristic Raman peaks between 722 and 723 and 917 and 919 cm 1.They exhibit a bimodal grain size distribution:large-crystals with average grain sizes greater than 100 μm and microcrystals less than 10 μm.The population of microcrystals increased with pressure,apparently due to the increase in over-pressure (the difference between the experimental pressure condition and the equilibrium transformation pressure at 1400°C),which promotes nucleation and retards grain growth.All run charges contained large numbers of wadsleyite microcrystals,because of the low activation energy of the nucleation process.The experimentally observed microstructure may shed light on the morphology of wadsleyite observed in shocked meteorites.At 19.5 GPa,wadsleyite coexisted with ringwoodite (γ) in Fo 100,but was absent in Fo 90.At 20 GPa,both samples transformed completely into ringwoodite,which was characterized by the 798 and 840 cm 1 Raman lines.Ringwoodite crystals are euhedral grains (average grain size 10-20 μm),with well-developed triple junctions.The complex upper mantle structure in eastern China determined from seismological studies cannot be explained by the simple transformation sequence of the olivine system alone.Phase transformations in other pyroxene-normative components (including pyroxenes and garnets) and the interaction of these components with olivine may be responsible for the complex structure.High-pressure and high-temperature experimental studies on complex systems (e.g.olivine-pyroxene),combined with data from geophysical exploration,may help in establishing a more realistic geological-petrological model for eastern China and further our understanding of the possible physical mechanisms that are responsible for the complex structure.Such studies will have profound implications for understanding the dynamic processes in the deep Earth interior.

Seismic wave velocity of Archaeozoic felsic rocks from North China and its existing location in the crust

This paper contains two contents. The first is seismic velocity of felsic crystalline rocks of North China at room temperature and high pressures and at both high temperatures and pressures. The second is heating acoustic emission of felsic rocks at atmosphere pressure and the temperature of the quartz (-( transition. The results of these experiments show that velocities of the felsic crystalline rocks are obviously lower than that of the basic rocks and no visible relationship with metamorphic phase. The velocity curves of rocks containing quartz display peaks of the (-( phase reaction, which are different from other rocks in configuration. When the heating temperature is up to the phase transition temperature of quartz at the atmosphere pressure, felsic hypometamorphic rocks and magma granite produce acoustic emission. While the other kind of the granite generated by metasomatism does not produce acoustic emission. These results have the following implications. It explains the crustal constitution of the North China craton in combination with other geoscientific data, and clarifies the existing space of ( quartz and ( quartz. It also indicates that the (-( quartz transition and dehydration melting of amphibole and biotite in the lower crustal rocks of the Cenozoic tectonic subsidence area are likely associated with faulting (tensional fault) and seismic activities.

固体氢在极端压强下的超导性能

氢元素在常压下具有最简单的晶体结构和物理性质。随着压强增加,氢单质发生相变,由绝缘体转变为金属,被称为金属氢。数值模拟表明,金属氢具有高温超导电性,因此,金属氢研究也被称为高压物理领域的“圣杯”课题。利用基于密度泛函理论的第一性原理计算方法,对固体氢在极端高压(0.5~5.0 TPa)下的结构和超导电性开展了系统研究。研究结果表明:固体氢的高压相变序列为I4_(1)/amd→oC12→cI16;对于同一种结构,随着压强增加,电声耦合系数减小,费米面处电子态密度减小,特征振动频率增加,超导转变温度发生小幅变化;在2.0 TPa压强下,固体氢的超导转变温度高达418 K(库伦赝势经验值μ^(*)=0.10)。研究工作将为金属氢及其超导电性的后续理论和实验研究提供参考。

金刚石/纳米氧化铝陶瓷复合材料高温高压合成物相结构分析

以正硅酸乙酯(TEOS)为反应前驱体,采用溶胶-凝胶法在金刚石微粉(粒度0.1~4μm)表面包覆一层非晶纳米氧化硅膜层,同时在覆膜层中加入纳米Si粉和纳米Al_(2)O_(3)粉,制备出金刚石/纳米SiO_(2)/纳米Al_(2)O_(3)复合包覆体。采用高温高压(HTHP)技术,将复合包覆材料置于六面顶压机中,以压力5 GPa、温度1100℃~1700℃、保温20 min的条件制备了金刚石-氧化铝陶瓷烧结体。在高温高压合成过程中,纳米SiO_(2)从非晶态转变为晶态,原料纳米Al_(2)O_(3)中的γ-相、θ-相转变为稳定的α-相,同时,SiO_(2)和Al_(2)O_(3)之间形成了Al_(2)SiO_(5)(莫来石)相,由此,通过高温高压下反应原料的结构转变与复合,可以获得致密度良好的金刚石-氧化铝复合材料。

碳纳米葱(OLC)与微米金刚石(MD)烧结制备纳米聚晶金刚石复合材料(nPCD)的表征分析

在4~6GPa/1000~1400℃/5~30min条件下,用微米金刚石(MD)和碳纳米葱(OLC)混合物作为原材料制备了纳米聚晶金刚石(nPCD)复合材料。采用XRD、FESEM、HRTEM、Archimedes原理和Vickers硬度计表征了nPCD复合材料的组成、形貌、微观结构、密度和硬度。研究了MD和烧结参数对nPCD复合材料的组成、微观结构、性能。结果表明,MD在nPCD复合材料中分布均匀。MD作为晶核促进OLC向金刚石的转换。烧结压力的增加提高了nPCD复合材料的密度和硬度。当烧结压力从4GPa提高到6GPa时,nPCD复合材料的密度从2.72g/cm^(3)增加到3.02g/cm^(3),硬度从41.85GPa增加到56GPa。提高烧结温度和延长保持时间使nPCD复合材料的密度和硬度先升高后降低。在nPCD复合材料中nPCD区域具有孪晶结构。孪晶结构的存在提高了nPCD复合材料的硬度。

高温高压含水凝析气相态特征研究

通过独立设计的含水凝析气相态测试方法,研究了含水凝析气相态特征及气态水对凝析气体系相态特征的影响。在高温、高压地层条件下,凝析气中气态水含量随压力的降低急剧增大,当压力降至7.5MPa时,气中的气态水含量高达539m3/104m3。气态水的存在使凝析气体系的露点压力降低了2.5MPa。随着定容衰竭过程地层压力的降低,地层水以气态形式被蒸发而进入凝析气中的含量不断增加,由于水相的强极性,气态水不但使凝析气中重质烃更多地发生反凝析,也使凝析气中较轻烃类组分发生反凝析。虽然气态水的存在降低了凝析气体系的露点压力,但是一旦突破露点压力,气态水明显地增大了反凝析液量,加重了凝析油的损失。定容衰竭实验结果表明,富含气态水的凝析气样反凝析液量大于无水凝析气样,含气态水的凝析气中凝析液的采出程度低于不含水的情况,并随压力降低,两组样品的反凝析液量和凝析液采出程度的差别越来越大。